Selective Photoexcitation Research Articles

Excitation-Wavelength-Dependent Photophysics of a Torsionally Disordered Push-Pull Dye.

The torsional disorder of conjugated dyes in the electronic ground state can lead to inhomogeneous broadening of the S1 ←S0 absorption band, allowing for the selective photoexcitation of molecules with different amounts of distortion. Here, we investigate how this affects electronic transitions to upper excited states. We show that torsion of a core-alkynylated push-pull dye can have opposite effects on the oscillator strength of its lowest-energy transitions. Consequently, photoselection of planar and twisted molecules can be achieved by exciting in distinct absorption bands. Whereas this has limited effect in liquids due to fast planarization of the excited molecules, it strongly affects the overall photophysics in a polymeric environment, where torsional motion is hindered, allowing for the photoselection of molecules with different fluorescence quantum yields and intersystem-crossing dynamics.

Unexpected Performance of a Bifunctional Sensitizer/Activator Component for Photon Energy Management via Upconversion.

We here report on the observation of upconverted photoluminescence (UC-PL) from the blue-light-emitting 9,10-diphenylanthracene (DPA) mixed with the yellow-light-absorbing bifunctional sensitizer/activator component of (3,3,7,8,12,13,17,18-octaethylporphyrin-22,24-diid-2-one) PtII (PtOEP-K). Yellow-to-blue UC-PL (0.680 eV spectral upshift) is achieved at room temperature under ultralow power continuous incoherent photoexcitation (220 μW/cm2) despite the absence of triplet energy transfer (TET) between PtOEP-K and DPA. Under selective CW-laser photoexcitation of PtOEP-K in DPA:PtOEP-K, a 2.5% UC-PL quantum yield is obtained; that is an improvement exceeding by more than 3 orders of magnitude the UC-PL quantum yield of TTA-UC material combinations wherein no TET is operative. The PL response of DPA:PtOEP-K to varying laser fluence suggests that bimolecular annihilation reactions between triplet-excited PtOEP-K facilitate the UC-PL activation in DPA. These findings pave the way toward low-complexity strategies for the reduction of transmission losses in solar energy technologies through an innovative wavelength upshifting protocol involving excitonic materials.

Spectral characterization of a blue light-emitting micro-LED platform on skin-associated microbial chromophores

The therapeutic application of blue light (380 – 500nm) has garnered considerable attention in recent years as it offers a non-invasive approach for the management of prevalent skin conditions including acne vulgaris and atopic dermatitis. These conditions are often characterised by an imbalance in the microbial communities that colonise our skin, termed the skin microbiome. In conditions including acne vulgaris, blue light is thought to address this imbalance through the selective photoexcitation of microbial species expressing wavelength-specific chromophores, differentially affecting skin commensals and thus altering the relative species composition. However, the abundance and diversity of these chromophores across the skin microbiota remains poorly understood. Similarly, devices utilised for studies are often bulky and poorly characterised which if translated to therapy could result in reduced patient compliance. Here, we present a clinically viable micro-LED illumination platform with peak emission 450 nm (17 nm FWHM) and adjustable irradiance output to a maximum 0.55 ± 0.01 W/cm2, dependent upon the concentration of titanium dioxide nanoparticles applied to an accompanying flexible light extraction substrate. Utilising spectrometry approaches, we characterised the abundance of prospective blue light chromophores across skin commensal bacteria isolated from healthy volunteers. Of the strains surveyed 62.5% exhibited absorption peaks within the blue light spectrum, evidencing expression of carotenoid pigments (18.8%, 420–483 nm; Micrococcus luteus, Kocuria spp.), porphyrins (12.5%, 402–413 nm; Cutibacterium spp.) and potential flavins (31.2%, 420–425 nm; Staphylococcus and Dermacoccus spp.). We also present evidence of the capacity of these species to diminish irradiance output when combined with the micro-LED platform and in turn how exposure to low-dose blue light causes shifts in observed absorbance spectra peaks. Collectively these findings highlight a crucial deficit in understanding how microbial chromophores might shape response to blue light and in turn evidence of a micro-LED illumination platform with potential for clinical applications.

Long-Lived Charge Separation in Single Crystals of an Electron Donor Covalently Linked to Four Acceptor Molecules.

Crystalline donor-acceptor (D-A) systems serve as an excellent platform for studying CT exciton creation, migration, and dissociation into free charge carriers for solar energy conversion. Donor-acceptor cocrystals have been utilized to develop an understanding of CT exciton formation in ordered organic solids; however, the strong electronic coupling of the D and A units can sometimes limit charge separation lifetimes due to their close proximity. Covalent D-A systems that preorganize specific donor-acceptor structures can assist in engineering crystal morphologies that promote long-lived charge separation to overcome this limitation. Here we investigate photogenerated CT exciton formation in a single crystal of a 2,5,8,11-tetraphenylperylene (PerPh4) donor to which four identical naphthalene-(1,4:5,8)-bis(dicarboximide) (NDI) electron acceptors are covalently attached at the para positions of the PerPh4 phenyl groups to yield PerPh4-NDI4. X-ray crystallography shows that the four NDIs pack pairwise into two distinct motifs. Two NDI acceptors of one PerPh4-NDI4 are positioned over the PerPh4 donors of adjacent PerPh4-NDI4 molecules with the donor and acceptor π-systems having a large dihedral angle between them, while the other two NDIs of PerPh4-NDI4 form xylene-NDI van der Waals π-stacks with the corresponding NDIs in adjacent PerPh4-NDI4 molecules. Upon selective photoexcitation of PerPh4 in the single crystal, CT exciton formation occurs in <300 fs yielding electron-hole pairs that live for more than ∼16 μs. This demonstrates the effectiveness of covalently linked D-A systems for engineering single crystal structures that promote efficient and long-lived charge separation for solar energy conversion.

Light-Quality-Adapted Carotenoid Photoprotection in the Photosystem of Roseiflexus castenholzii.

The photosystem of filamentous anoxygenic phototroph Roseiflexus (Rfl.) castenholzii comprises a light-harvesting (LH) complex encircling a reaction center (RC), which intensely absorbs blue-green light by carotenoid (Car) and near-infrared light by bacteriochlorophyll (BChl). To explore the influence of light quality (color) on the photosynthetic activity, we compared the pigment compositions and triplet excitation dynamics of the LH-RCs from Rfl. castenholzii was adapted to blue-green light (bg-LH-RC) and to near-infrared light (nir-LH-RC). Both LH-RCs bind γ-carotene derivatives; however, compared to that of nir-LH-RC (12%), bg-LH-RC contains substantially higher keto-γ-carotene content (43%) and shows considerably faster BChl-to-Car triplet excitation transfer (10.9 ns vs 15.0 ns). For bg-LH-RC, but not nir-LH-RC, selective photoexcitation of Car and the 800 nm-absorbing BChl led to Car-to-Car triplet transfer and BChl-Car singlet fission reactions, respectively. The unique excitation dynamics of bg-LH-RC enhances its photoprotection, which is crucial for the survival of aquatic anoxygenic phototrophs from photooxidative stress.

Ultrafast Charge Transfer Dynamics in a Slip-Stacked Donor-Acceptor-Acceptor System.

Photoexcitation of molecular electron donor and/or acceptor chromophore aggregates can greatly affect their charge-transfer dynamics. Excitonic coupling not only alters the energy landscape in the excited state but may also open new photophysical pathways, such as symmetry-breaking charge separation (SB-CS). Here, we investigate the impact of excitonic coupling on a covalent donor-acceptor-acceptor system comprising a perylene donor (Per) and two perylenediimide (PDI) acceptor chromophores in which the three components are π-stacked in a geometry that is slipped along their long axes (Per-PDI2). Following selective photoexcitation of PDI, femtosecond transient absorption data for Per-PDI2 is compared to that for the single-donor, single-acceptor Per-PDI system, and the PDI2 dimer, which both have the same interchromophore geometry as Per-PDI2. The data show that electron transfer from Per to the lower exciton state of the PDI dimer is slower than that of the single PDI acceptor system. This is due to the lower free energy of the reaction for charge separation because of the electronic stabilization afforded by the excitonic coupling between the PDIs. While PDI2 was shown previously to undergo ultrafast SB-CS, the strong π-π electronic interaction of Per with the adjacent PDI in Per-PDI2 breaks the electronic symmetry of the PDI dimer, resulting in the oxidation of Per rather than SB-CS. These results show that the electronic coupling between molecules designed to accept charges produced by SB-CS in molecular dimers and the chromophores comprising the dimer must be balanced to favor SB-CS.

Harvesting electrons and holes from photodriven symmetry-breaking charge separation within a perylenediimide photosynthetic model dimer.

Understanding how to utilize symmetry-breaking charge separation (SB-CS) offers a path toward increasingly efficient light-harvesting technologies. This process plays a central role in the first step of photosynthesis, in which the dimeric "special pair" of the photosynthetic reaction center enters a coherent SB-CS state after photoexcitation. Previous research on SB-CS in both biological and synthetic chromophore dimers has focused on increasing the efficiency of light-driven processes. In a chromophore dimer undergoing SB-CS, the energy of the radical ion pair product is nearly isoenergetic with that of the lowest excited singlet (S1) state of the dimer. This means that very little energy is lost from the absorbed photon. In principle, the relatively high energy electron and hole generated by SB-CS within the chromophore dimer can each be transferred to adjacent charge acceptors to extend the lifetime of the electron-hole pair, which can increase the efficiency of solar energy conversion. To investigate this possibility, we have designed a bis-perylenediimide cyclophane (mPDI2) covalently linked to a secondary electron donor, peri-xanthenoxanthene (PXX) and a secondary electron acceptor, partially fluorinated naphthalenediimide (FNDI). Upon selective photoexcitation of mPDI2, transient absorption spectroscopy shows that mPDI2 undergoes SB-CS, followed by two secondary charge transfer reactions to generate a PXX•+-mPDI2-FNDI•- radical ion pair having a nearly 3 µs lifetime. This strategy has the potential to increase the efficiency of molecular systems for artificial photosynthesis and photovoltaics.

Direct observation of chirality-induced spin selectivity in electron donor-acceptor molecules.

The role of chirality in determining the spin dynamics of photoinduced electron transfer in donor-acceptor molecules remains an open question. Although chirality-induced spin selectivity (CISS) has been demonstrated in molecules bound to substrates, experimental information about whether this process influences spin dynamics in the molecules themselves is lacking. Here we used time-resolved electron paramagnetic resonance spectroscopy to show that CISS strongly influences the spin dynamics of isolated covalent donor-chiral bridge-acceptor (D-Bχ-A) molecules in which selective photoexcitation of D is followed by two rapid, sequential electron-transfer events to yield D•+-Bχ-A•-. Exploiting this phenomenon affords the possibility of using chiral molecular building blocks to control electron spin states in quantum information applications.

Quantum Sensing of Electric Fields Using Spin-Correlated Radical Ion Pairs.

Quantum sensing affords the possibility of using quantum entanglement to probe electromagnetic fields with exquisite sensitivity. In this work, we show that a photogenerated spin-correlated radical ion pair (SCRP) can be used to sense an electric field change created at one radical ion of the pair using molecular recognition. The SCRP is generated within a covalent donor-chromophore-acceptor system PXX-PMI-NDI, 1, where PXX = peri-xanthenoxanthene, PMI = 1,6-bis(p-t-butylphenoxy)perylene-3,4-dicarboximide, and NDI = naphthalene-1,8:4,5-bis(dicarboximide). The electron-rich PXX donor in 1 acts as a guest molecule that can be encapsulated selectively by a tetracationic cyclophane ExBox4+ host to give a supramolecular complex 1 ⊂ ExBox4+. Selective photoexcitation of the PMI chromophore results in ultrafast generation of the PXX•+-PMI-NDI•- SCRP. When PXX is encapsulated by ExBox4+, the cyclophane generates an electric field that repels the positive charge on PXX•+ within PXX•+-PMI-NDI•-, reducing the SCRP distance, i.e., the distance between the centers-of-charge on the donor and acceptor. Pulse-EPR measurements are used to measure the coherent oscillations created primarily by the electron-electron dipolar coupling in the SCRP, which yields the distance between the two charges (spins) of PXX•+-PMI-NDI•-. The experimental results show that the distance between PXX•+ and NDI•- decreases when ExBox4+ encapsulates PXX•+, which demonstrates that the SCRP can function as a quantum sensor to detect electric field changes in the vicinity of the radical ions.

Quantum Gate Operations on a Spectrally Addressable Photogenerated Molecular Electron Spin-Qubit Pair

Sub-nanosecond photodriven electron transfer from a molecular donor to an acceptor can be used to generate a radical pair (RP) having two entangled electron spins in a well-defined pure initial singlet quantum state to serve as a spin-qubit pair (SQP). Achieving good spin-qubit addressability is challenging because many organic radical ions have large hyperfine couplings (HFCs) in addition to significant g-anisotropy, which results in significant spectral overlap. Moreover, using radicals with g-factors that deviate significantly from that of the free electron results in difficulty generating microwave pulses with sufficiently large bandwidths to manipulate the two spins either simultaneously or selectively as is necessary to implement the controlled-NOT (CNOT) quantum gate essential for quantum algorithms. Here, we address these issues by using a covalently linked donor-acceptor(1)-acceptor(2) (D-A1-A2) molecule with significantly reduced HFCs that uses fully deuterated peri-xanthenoxanthene (PXX) as D, naphthalenemonoimide (NMI) as A1, and a C60 derivative as A2. Selective photoexcitation of PXX within PXX-d9-NMI-C60 results in sub-nanosecond, two-step electron transfer to generate the long-lived PXX•+-d9-NMI-C60•- SQP. Alignment of PXX•+-d9-NMI-C60•- in the nematic liquid crystal 4-cyano-4'-(n-pentyl)biphenyl (5CB) at cryogenic temperatures results in well-resolved, narrow resonances for each electron spin. We demonstrate both single-qubit gate and two-qubit CNOT gate operations using both selective and nonselective Gaussian-shaped microwave pulses and broadband spectral detection of the spin states following the gate operations.

Theranostic FRET Gate to Visualize and Quantify Bacterial Membrane Breaching.

Designing new antimicrobial-cum-probes to study real-time bacterial membrane breaching and concurrently developing inquisitorial image-based analytical tools is essential for the treatment of infectious diseases. An array of aggregation-induced emission (AIE) polymers (donor) consisting of neutral, anionic, and cationic charges were designed and employed as antimicrobial theranostic gatekeepers for the permeabilization of the peptidoglycan layer-adherable crystal violet (CV, acceptor). An AIE-active tetraphenylethylene (TPE)-tagged polycaprolactone biodegradable platform was chosen, and their self-assembled tiny amphiphilic nanoparticles were employed as a gatekeeper in the construction of bacterial membrane-reinforced fluorescent resonance energy transfer (FRET) probes. Electrostatic adhering of the cationic AIE polymer and subsequent gate opening aided fluorescent FRET probe activation on the membrane of Gram-negative bacteria, Escherichia coli. The selective photoexcitation energy transfer process in confocal microscopy experiments facilitated the building of a visualization-based FRET assay for the quantification of bactericidal activity. Nonantimicrobial AIE polymers (neutral and anionic) did not breach the bacterial membrane, resulting in no FRET signal. Detailed photophysical studies were done to establish the FRET probe mechanism, and a proof of concept was established.

Optical Initialization of Molecular Qubit Spin States Using Weak Exchange Coupling to Photogenerated Fullerene Triplet States.

The ability to initialize an electron spin qubit into a well-defined state is an important criterion for quantum information applications. To achieve this goal, a chromophore photoexcited to its triplet state is used to strongly spin polarize a nearby stable radical in a series of C60 fullerene derivatives containing a covalently linked α,γ-bisdiphenylene-β-phenylallyl (BDPA) radical. Selective photoexcitation of C60 results in up to 20-fold enhancement of the BDPA spin polarization observed by pulse electron paramagnetic resonance spectroscopy at room temperature. The sign of the spin polarization depends on the nature of the molecular spacer between C60 and BDPA. In addition, transient absorption spectroscopy and pulse-EPR measurements reveal that the BDPA spin polarization is derived from spin polarization transfer from the C60 triplet state by weak exchange coupling over a 1 nm distance.

Polariton drag enabled quantum geometric photocurrents in high-symmetry materials

Lowered symmetry enables access to a wide set of responses not typically accessible in high symmetry materials. Prime examples are time-reversal forbidden quantum geometric photocurrent responses (e.g., linear injection and circular shift photocurrents) that are thought to vanish in nonmagnetic materials. Here we argue that polariton drag processes enable to unblock such quantum geometric photocurrents even in nonmagnetic and centrosymmetric materials. Strikingly, we uncover how a cooperative effect between finite $\mathbf{q}$ irradiation and the Fermi surface position leads to a polariton selective photoexcitation (PSP). PSP enables to directly address carriers within tight momentum resolved windows of the Fermi surface to yield giant enhancements of quantum geometric photocurrents. This selectivity enables to directly track momentum resolved quantum geometric quantities along the Fermi surface providing a new tool to interrogate the quantum geometry of high symmetry materials.

Charge transfer dynamics and interlayer exciton formation in MoS2/VOPc mixed dimensional heterojunction.

Mixed-dimensional van der Waals heterojunctions involve interfacing materials with different dimensionalities, such as a 2D transition metal dichalcogenide and a 0D organic semiconductor. These heterojunctions have shown unique interfacial properties not found in either individual component. Here, we use femtosecond transient absorption to reveal photoinduced charge transfer and interlayer exciton formation in a mixed-dimensional type-II heterojunction between monolayer MoS2 and vanadyl phthalocyanine (VOPc). Selective excitation of the MoS2 exciton leads to hole transfer from the MoS2 valence band to VOPc highest occupied molecular orbit in ∼710fs. On the contrary, selective photoexcitation of the VOPc layer leads to instantaneous electron transfer from its excited state to the conduction band of MoS2 in less than 100fs. This light-initiated ultrafast separation of electrons and holes across the heterojunction interface leads to the formation of an interlayer exciton. These interlayer excitons formed across the interface lead to longer-lived charge-separated states of up to 2.5ns, longer than in each individual layer of this heterojunction. Thus, the longer charge-separated state along with ultrafast charge transfer times provide promising results for photovoltaic and optoelectronic device applications.

Tunable diamond raman lasers for resonance photo-ionization and ion beam production

Lasers with wide tunability and tailored linewidth are key assets for spectroscopy research and applications. We show that diamond, when configured as a Raman laser, provides agile access to a broad range of wavelengths while being capable of efficient and selective photo-excitation of atomic species and suitable spectroscopic applications thanks to its narrow linewidth. We demonstrate the use of a compact diamond Raman laser capable of efficient ion beam production by resonance ionization of Sm isotopes in a hot metal cavity. The ionization efficiency was compared with a conventional Ti:sapphire laser operating at the same wavelength. Our results show that the overall ion current produced by the diamond Raman laser was comparable -or even superior in some cases-to that of the commonly used Ti:sapphire lasers. This demonstrates the photo-ionization capability of Raman lasers in the Doppler broadening-dominated regime, even with the considerable differences in their spectral properties. In order to theoretically corroborate the obtained data and with an eye on studying the most convenient spectral properties for photo-ionization experiments, we propose a simple excitation model that analyzes and compares the spectral overlap of the Raman and Ti:Sapphire lasers with the Doppler-broadened atomic spectral line. We demonstrate that Raman lasers are a suitable source for resonance photo-ionization applications in this regime.

Ultrafast hot carrier transfer in WS2/graphene large area heterostructures

Charge transfer processes in two-dimensional van der Waals heterostructures enable upconversion of low energy photons and efficient charge carriers extraction. Here we use broadband ultrafast optical spectroscopy to track charge transfer dynamics in large-area 2D heterostructures made of epitaxial single-layer tungsten disulfide (WS2) grown by chemical vapour deposition on graphene. Selective carrier photoexcitation in graphene, with tunable near-infrared photon energies as low as 0.8 eV (i.e. lower than half of the optical bandgap of WS2), results in an almost instantaneous bleaching of the WS2 excitonic peaks in the visible range, due to the interlayer charge transfer process. We find that the charge transfer signal is strongly non-linear with the pump fluence and it becomes progressively more linear at increasing pump photon energies, while the interlayer photoinjection rate is constant in energy, reflecting the spectrally flat absorbance of graphene. We ascribe the interlayer charge transfer to a fast transfer of hot carriers, photogenerated in graphene, to the semiconducting layer. The measured sub-20-fs hot-carrier transfer sets the ultimate timescale for this process. Besides their fundamental interest, our results are technologically relevant because, given the capability of large-area deterministic growth of the heterostructure, they open up promising paths for novel 2D photodetectors, also potentially scalable to industrial platforms.

Selective photo-excitation of molecules enabled by stimulated Raman pre-excitation.

Double resonance excitation, where the energies of vibrational and electronic molecular transitions are combined in a single, sequential excitation process, was introduced in the 1970s but has only been recently applied to microscopy due to the immense progress in Raman spectroscopy. The value of the technique is in combining the chemical selectivity of IR or Raman excitation with the much larger cross-sections of electronic transitions. Recently, it has been shown to be particularly suited for the detection and identification of chromophores at low concentrations and in the presence of spectral crosstalk. However, despite its low quantum yield per pulse sequence, we believe the technique has potential for selective photochemical transformations. There are some cases (e.g., the selective excitation of optogenetic switches) where the low yield may be overcome by repeated excitations to build up biochemically relevant concentrations. Here we show that double resonance excitation using general, non-resonant Raman pre-excitation is a viable candidate for selectively promoting molecules to chemically active energy levels. The use of non-resonant Raman pre-excitation is less constraining than resonant Raman (used in previous double resonance microscopy works) since the choice of Raman pump-Stokes frequencies may be rather freely chosen.

Self-Reporting Polysaccharide Polymersome for Doxorubicin and Cisplatin Delivery to Live Cancer Cells.

We report self-reporting fluorescent polysaccharide polymersome nanoassemblies for enzyme-responsive intracellular delivery of two clinical anticancer drugs doxorubicin (DOX) and cisplatin to study the real-time drug-releasing aspects by fluorescent resonance energy transfer (FRET) bioimaging in live cancer cells. Fluorescent polymersomes were tailor-made by tagging an aggregation-induced emission (AIE) optical chromophore, tetraphenylethylene (TPE), and a plant-based vesicular directing hydrophobic unit through enzyme-biodegradable aliphatic ester chemical linkages in the polysaccharide dextran. The blue-luminescent polymersome self-assembled in water and exhibited excellent encapsulation capability for the red-luminescent anticancer drug DOX. FRET between the AIE polymersome host and DOX guest molecules resulted in a completely turn-off probe. At the intracellular level, the lysosomal enzymatic disassembly of the polymersome restored the dual fluorescent signals from DOX and TPE at the nucleus and the lysosomes, respectively. Live-cell confocal microscopy coupled with selective photoexcitation was employed to study the real-time polymersome disassembly by monitoring the turn-on fluorescent signals in human breast cancer cell lines. Alternatively, carboxylic acid-functionalized AIE polymersomes were also tailor-made for cisplatin stitching to directly monitor Pt drug delivery. The polymersome nanoassemblies exhibited excellent structural tolerance for the chemical conjugation of the Pt drugs, and the fluorescence signals were unaltered. An in vitro drug release study confirmed that the cisplatin-stitched fluorescent polymersomes were very stable under physiological conditions and underwent lysosomal enzymatic degradation to inhibit the cancer cell growth. A lysosomal colocalization experiment using confocal microscopy substantiates the enzyme-responsive degradation of these polymersomes to release both the encapsulated and conjugated drugs at the intracellular level. The present design provides a unique opportunity to deliver more than one anticancer drug from a single polymersome platform in cancer research.

Design and Construction of an Optical TEM Specimen Holder

Abstract:Electron microscopy has enabled atomic resolution imaging of matter. However, unlike optical spectroscopic imaging, traditional electron microscopes provide limited spectroscopic information in terms of their energy resolution. Only recently, owing to advances in monochromated STEM-EELS, have transmission electron microscopes (TEMs) been able to attain a high energy resolution. We recently proposed combining spectrally selective photoexcitation with HRTEM to achieve sub-nanometer scale optical imaging, a technique we called photoabsorption microscopy using electron analysis (PAMELA). To realize PAMELA-TEM experimentally, we constructed a TEM holder with an optical feedthrough, capable of photoexciting materials with different wavelengths. In this article, we describe our process for designing and fabricating an optical TEM specimen holder, highlighting important aspects of the design.

Inversion of the Deactivation Efficiency of Excited States upon Selective Photoexcitation of the Uranyl Ion Complex with D-Tryptophan in Aqueous and Methanol Solutions

Inversion of the Deactivation Efficiency of Excited States upon Selective Photoexcitation of the Uranyl Ion Complex with D-Tryptophan in Aqueous and Methanol Solutions